Composition of matter and processes for the manufacture of the same



i 10 (1878)), andDiversandJ-Iaga (J ch s 9 Water was added with cooling to 114. parts of 53 1O 35 formed as an intermediate; but in the presence of 45 titanyl sulfamate remains in solution. Of these 55 cipi ion of h sulfamate- F r m ny purposes swelled but remained in the a er; I 55 Patented Dec. 26, 1939 Charles W. J. Wende, -Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Dcl., a corporation of Delaware No Drawing. Application April 7, 1938,

Serial No. 200,747

Claims. (-1. 23-50) This invention relates to a new and useful the titanyl sulfamate solution may be used directcomposition of inattenthetitanyl salt-of sulfamic i y without'isolaliion 0f the 83113111801161 form- .acid, and the method of its manufacture. 1 The foll w ng e p i which the parts r It has long beenknown that the sulfamic acid W i unless Otherwise p ifi l s rate 5 salts of metals which :form basic oxides or hythe preparation f titanyl sulfamatei. 5

drc-xides, are easily prepared bysimple reaction of thebasic Oxide orhydroxide with sulfamic Fi I acid as described in the chemical literature by solution comprlsmg 200 parts lead Sulfamate E. Berglund n Soc. Chim 2 9 22 Pb(SO3NH2)2 dissolved in about 200parts cold 1645 (1396)), H it is reported in t per cent titanium chloride solution. The lead.

literature that the sulfa-mic acid salts of metals chloride r c t was filtered Off after stand- I which form neutral or acidic oxides and hymg about One T101111 p addition f droxides, g, bi th, t arsenic, antimony .methanol (1 volume) and acetone (2 volumes) a iron (ferric), and the like, cannot be prepared White precipitate 0f titanyl Sulfamate formed 15 because of the great ease and rapidity with which Which Was removed y filt at on, Washed With such salts are hydrolyzed in aqueous solution. Q L and-dried Without heating?- Evaporation Thus, the art has n t heretofore b apprised of the clear filtrate under reduced pressure yielded of any titaniumsalts of sulfamic acid, especially Sulfamic acid- The acetone precipitated Product since titanium oxide does not react with sulfamic When fi l t in Waller gavte no reaction w t 20 acid even upon warming or prolonged contact potassium iodide or silver nitrate thereby indi- With a saturated sulfarnic acid solution. Moreeating the absence of lead and chloride salts. over, had u h a ti b possible it would The presence of free sulfamic acid in the filtrate" be expected from the experience with th residues indicated that titanium sulfamate had photeric metals that rapid hydrolysis would t hydrolyzed to titanyl sulfamate (TiO(SOs NH2 )z).

place in aqueous solution. Solutions of the latter salt prec1p1tated titanium I have now found that by reacting in aqueous Oxide i solution a titanium salt and a sulfamate, the Eiwmple U cation of which forms a Water-insoluble salt with Fourteen '(14) partsof titanyl Sulfate e the anion or the titanium salt, a basic titanium 30) salt of sulfamic acid is formed and remains in (TiOSOWZHzO) solution iron: which it may be isolated by addition nan-solvents or by other suitable means. Possibly the normal titanium sulfamate. is first was dissolved in about 150 parts water and to this solution was added a solution of 19.5parts lead sulfamate, Pb(SO3NHz) 2 dissolved in parts of water. After standing for a short period the 35 precipitated lead sulfate was removed by filtra- I tion. The titanyl sulfamate, TiO(SO3NI-Iz)2, was then precipitated from the clear filtrate by the addition of about 2 volumes methanol and 2 volumes acetone. The precipitate was gelatinous in character. It was collected on-a filter and allowed ,to dry Without heating. Nofree sulfamic acid was observed in the filtrate, indicating that hy- I drolysis had not progressed beyond the titanyl stage. The final dry product was a white powder which was readily soluble in water. When a water solution of titanyl sulfamate was heated the salt was hydrolyzed, a white precipitate of titanium. oxide being formed. v

Paper impregnated with titanyl sulfamate in water is immediately hydrolyzed to a soluble titanyl sulfamate. The titanyl sulfamate may be further hydrolyzed to precipitate hydrated titanium oxide if the salt solution is heated.

"file reaction, for example, may be carried out with titanium sulfate or titanyl sulfate as the titanium salt and with barium sulfamate or lead sulfamate as the sulfamate. The insoluble barium or lead sulfate is precipitatedwhile the soluble two reagents, barium sulfamate is preferred on economic grounds, altho lead sulfa-mate forms a more readily separated precipitate. Strontium and calcium sulfamates may be used in instances where the slight solubility of their sulfates is not objectionable. In any case, the titanyl sulfamate solution and dried became tiff d d parchfo med may be isolated by evapflation of the mentized appearance. When the treated paper solution under conditions of low heat or by the was heated and egeinvpl'aeed i-e th tit addition of such organic solvents as cause prenium present in the paper formed a gel Whic Various salts of titanium may be used for the preparation of titanyl sulfamate providing that the anion of the titanium salt combines with the cation of the sulfamate to form an insoluble salt which may be removed by filtration, centrifuging, or similar procedures. The titanyl suliamate which remains in solution may be isolated by evaporation of the solution, or by pre cipitation by means of organic solvents, or by other well known methods of reducing solubility of a salt in water. For many uses, it is not necessary to isolate the titanyl sulfamate since the solutions prepared by the methods given maybe used for many purposes as such. In such case it may be desirable partially to neutralize any excess sulfamic acid by addition of a suitably reactive base.

Still another way to make titanyl sulfamate is to react potassium titanium sulfate in aqueous solution with a sulfamate, such as calcium sulfamate, the cation of which forms a sulfate relatively insoluble in Water and thereafter, if desired, precipitating any of the cation remaining in solution as a soluble salt. For example, any calcium remaining in solution may if desired be precipitated and disposed of as the oxalate.

The above description and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms with the spirit of the invention is intended to be included within the scope of the claims.

Titanyl sulfamate shows the property of being comparatively stable in aqueous solutions at ordinary temperature but readily hydrolyzing at increased temperatures. Hence, porous materials such as paper may be impregnated with solutions of titanyl sulfamate. Upon drying such impregnated materials by means of heating, titanium oxide is precipitated within the treated object. The acid formed by hydrolysis may be extracted by washing with water, which treatment does not appreciably remove the precipitated titanium oxide; or it may be hydrolyzed to ammonium acid sulfate by continued heating in the presence of water, and removed by washing or precipitated as an insoluble sulfate. Titanyl sulfamate may also be used for the tanning of leather, or for the preparation of titanium pigments.

I claim:

l. The method of preparing a basic sulfamate oft-etravalent titanium which comprises reacting in aqueous solution titanium tetrachloride and a sulfamate the cation of which forms an I insoluble chloride.

2. A basic salt of tetravalent titanium and sulfamic acid.

3. Titanyl sulfamate.

CHARLES W. J. WENDE. 

